1,2,3-Triazole carboxylic acid amides and biocidal compositions containing the same

ABSTRACT

1,2,3-Triazole carboxylic acid amides, of the formula ##STR1## in which R 1 , R 2 , R 3 , R 4  and n have the meaning defined in the specification in connection with formula I. The compounds have a broad biocidal, particularly herbicidal, insecticidal, acaricidal, fungicidal and nematocidal activity. They have a high degree of selectivity towards agriculturally valuable plants.

BACKGROUND OF THE INVENTION

The invention relates to 1,2,3-triazole carboxylic acid amides and aprocess for making these compounds and relates also to biocidalcomposition containing these compounds, particularly compositions havingherbicidal, insecticidal, acaricidal, fungicidal and/or nematocidalactivity.

1,2,4-triazole derivatives having a herbicidal activity already known(U.S. Pat. No. 3,952,001). Among theseN-ethyl-N-propyl-3(propylsulfonyl)-1H-1,2,4-triazole-1-carboxamide isdistinguished by its action against gramineous weeds. This compound,however, has the shortcoming of an insufficient compatibility foragricultural plants such as maize and cotton.

1,2,3-triazole derivatives having the above-mentioned activity and thethus existing utility have not become known heretofore to the knowledgeof these applicants.

It is, therefore, an object of the present invention to provide for newtriazole derivatives and for a process for making them which have abroad spectrum of applications particularly in the area of plantprotection.

SUMMARY OF THE INVENTION

This object is met by compounds constituted by 1,2,3-triazole carboxylicacid amides of the formula ##STR2## in which R₁ is C₁ -C₁₀ -alkyl, C₂-C₈ -alkenyl or -alkinyl, or is an aryl C₁ -C₃ -alkyl which may besubstituted in one or several positions by C₁ -C₆ -alkyl and/or halogenand/or C₁ -C₆ -alkoxy and/or nitro and/or trifluoromethyl;

R₂ is hydrogen or C₁ -C₁₀ alkyl of which the chain may be interrupted inone or several places by oxygen or sulfur and which may be substitutedby halogen;

R₃ and R₄ may be the same or different and may each be hydrogen, C₁ -C₁₀-alkyl, C₁ -C₁₀ -alkyl which may be substituted by halogen or C₁ -C₃-alkoxy, C₂ -C₃ -alkenyl or alkinyl, aryl-C₁ -C₃ -alkyl which may besubstituted in one or several positions by C₁ -C₆ -alky and/or halogenand/or C₁ -C₆ -alkoxy and/or nitro and/or trifluoromethyl, a C₃ -C₈-cycloaliphatic hydrocarbon group, a C₃ -C₈ cycloaliphatic hydrocarbongroup which may be substituted in one or several places by C₁ -C₆-alkyl, an aromatic hydrocarbon group which may be substituted in one orseveral positions by C₁ -C₆ -alkyl and/or halogen and/or C₁ -C₆ -alkoxyand/or nitro and/or trifluoromethyl, or in which

R₃ and R₄ together with the adjoining nitrogen atom may constitute a 3to 7 member ring which may include further O--, S-- or N-- atoms, and inwhich

n is 0, 1 or 2.

The compounds of the invention have a very broad biocidal activity. Theyare particularly distinguished by their herbicidal, insecticidal,acaricidal, fungicidal and/or nematocidal action which permits manydifferent uses thereof in the area of plant protection.

Depending on the particular significance of the substituents there maythus be particularly important utilities in which the compounds exhibita prominent action. Thus, the compounds may be used optionally asselective herbicides, plant growth regulators, insecticides, acaricides,fungicides or nematicides.

PREFERRED HERBICIDAL COMPOSITIONS

Among the compounds of the invention those are particularlydistinguished by their herbicidal activity in which in the generalformula I

R₁ is alkyl of 1 to 10 carbon atoms, for instance methyl, ethyl, propyl,isopropyl, butyl, sec.-butyl, isobutyl, pentyl or isopentyl, or isaryl-C₁ -C₃ -alkyl which may be substituted by chlorine such as benzyl,4-chlorobenzyl or 3,4-dichlorobenzyl,

R₂ is hydrogen, methyl, ethyl, propyl, isopropyl, butyl or tert.-butyl,

R₃ is alkyl, alkenyl or alkinyl of up to 6 carbon atoms which may besubstituted by chlorine or methoxy, for instance methyl, ethyl,2-chloroethyl, 2-methoxyethyl, propyl, isopropyl, 3-chloropropyl,3-methoxypropyl, butyl, sec.-butyl, isobutyl, pentyl, isopentyl, hexyl,allyl, 2-methylallyl, propino-2-yl, or cycloalkyl, e.g., cyclohexyl, and

R₄ is alkyl, alkenyl or alkinyl or up to 6 carbon atoms which may besubstituted by chlorine or methoxy, for instance methyl, ethyl,2-chloroethyl, 2-methoxyethyl, propyl, isopropyl, 3-methoxypropyl,3-chloropropyl, butyl, sec.-butyl, isobutyl, pentyl, isopentyl, hexyl,allyl, 2-methylallyl, or propino-2-yl, or cycloalkyl, e.g. cyclohexyl,or is aryl-C₁ -C₃ -alkyl which may be substituted by chlorine or methyl,for instance benzyl, 4-chlorobenzyl or 4-methylbenzyl or is an aromatichydrocarbon group which may be substituted by halogen or methyl, forinstance phenyl, 4-chlorophenyl, 4-methylphenyl, or 4-fluorophenyl, or

R₃ and R₄ together with the adjoining nitrogen atom constitute themorpholino-, piperidino-, pyrrolidino- or hexamethyleneimino group, and

n is 2.

These compounds have the advantage over the prior art compounds thatthey have a broad range of selectivity towards agricultural plants quiteapart from their high activity against mono- and a few dicotyl weeds.They also have a broad herbicidal activity when applied in the soil andcan be used against mono- and dicotyl weeds in pre-emergence andpost-emergence application. The compounds are effective also againstweeds such as Avena fatua, Alopecurus myosuroides, Echinochloa crusgalli, Digitaria sanguinalis, Cyperus esculentus, Sorghum halepense, Poaannua, Stellaria media, Senecio vulgaris, Amaranthus retroflexus,Polygonum lapathifolium and other weeds.

When used against weeds they are normally empolyed in amounts of 0.6 kgof active agent per about 2.5 acres up to 5 kg of active agent for thesame area. The compounds of the invention in these cases areparticularly selective against agricultural plants such as maize,cotton, potatoes, soy beans, peas and bush beans.

In addition, the compounds just discussed and also other compoundscoming under the formula I have growth regulating properties.

The visually discernible morphological changes always presuppose amodification of the physiological and biochemical processes in theplant, for instance the compounds of the invention stimulate thefollowing changes in the development of the plants:

Retardation of the vertical growth

Retardation of the root development

Intensification of the formation of plant pigments

Induction or promotion of the falling of the leaves.

The compounds of the invention can either be used alone or in mixturewith each other or admixed with other active agents. If desired, otherplant protection agents or pesticides may be added.

If a broadening of the activity range is intended it is possible also toadd other herbicides. For instance, herbicidally active mixturecomponents may be obtained from the group of the triazines,aminotriazoles, anilides, diazines, uraciles, aliphatic carboxylic acidsand halogenated carboxylic acids, substituted benzoic acid andaryloxycarboxylic acids, hydrazides, amides, nitriles, esters of suchcarboxylic acids, carbamic acid- and thiocarbamic acid esters, ureaderivatives, 1,3,6-trichlorobenzyloxypropanil and thiocyanate containingagents among others.

This reference to other additives should be understood to comprise alsononphytotoxic additives which in herbicides result in a synergisticactivity increase such as wetting agents, emulsifiers, solvents and allthe additives.

Preferred Insecticidal and Acaricidal Compounds

By their insecticidal and/or acaricidal activity are particularlydistinguished those compounds in which in the formula I R₁ is methyl,ethyl, propyl, allyl, or propinyl-2-yl, R₂ is hydrogen, methyl, ethyl,propyl, butyl or tert.-butyl, R₃ is hydrogen or methyl, and R₄ is methyland n is 0.

These compounds have a broad insecticidal and/or acaricidal activity. Aparticular advantage lies in their high initial action.

The compounds of the invention can be used against a multiplicity ofeconomically very significant pests, particularly from the systems ofthe dipterons, coleopterans, rhynchotans and orthopterans.

The compounds discussed are particularly effective at the usualconcentrations as used in industrial practice of 0.5 and less than0.01%.

Particularly distinguished among the compounds of the invention is the4-methyl-5-methylthio-1,2,3-triazole-1 (2,3)-carboxylic aciddimethylamide.

These compounds likewise can either be used alone or intermixed witheach other or in mixture with other active agents. Depending on theparticular purpose other plant protection agents may be added as well asactivity increasing additives such as solvents, wetting agents and oils.

Preferred Nematicidal compositions

A nematicidal effect is possessed particularly by those compounds inwhich in the formula I

R₁ is alkyl of 1 to 10 carbon atoms, for instance methyl, ethyl, propyl,isopropyl, butyl, sec.-butyl, isobutyl, tert.-butyl, pentyl, isopentyl,allyl, 2-methylallyl, propine-2-yl, or is aryl-C₁ -C₃ -alkyl which maybe substituted by chlorine, for instance benzyl, 4-chlorobenzyl or3,4-dichlorobenzyl,

R₂ is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl,isobutyl or tert.-butyl,

R₃ is hydrogen, alkyl, alkenyl or alkinyl of up to 6 carbon atoms, forinstance methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl,tert.-butyl, allyl or propino-2-yl,

R₄ is alkyl, alkenyl or alkinyl with up to 6 carbon atoms for instancemethyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, isobutyl,tert.-butyl, allyl or propino-2-yl, and

n is 0.

These compounds have surprisingly no phytotoxic effect in the amountsused in practical application. Therefore negative impacts on the plantgrowth do not occur.

When used against nematodes the compounds are preferably used in amountsof 10 to 50 kg of active agent per about 2.5 acres of soil and areapplied in a uniform manner and subsequently worked into the soil.

Among the phytopathogenic nematodes for which the compounds of theinvention are useful are for instance the families of the migrating rootnematodes Tylenchorhynchus, Pratylenchus, Paratylenchus,Heliocotylenchus, Xiphinema, Trichodorus and Longidorus; root gallnematodes as for instance Meloidogyne incognita, Meloidogyne hapla,Meloidogyne arenaria.

The active agents can be used for this purpose as such in the form oftheir formulations proper or in the form of application compositionsmade therefrom, such as solutions for actual use, emulsifiableconcentrations, emulsions, suspensions, spray powders, pastes andgranulates. The application is carried out in conventional form, forinstance by pouring, spraying, gasifying, smoking, dusting, etc.

Preferred Fungicidal Compositions

A fungicidal effect is characteristic for all compounds of the generalformula I and this both in treating the plants and in applying thecompounds to the seeds of the plants. The compounds of the inventionconstitute a particular technical advance because they open up newalternative possibilities where a prior art fungicide either is nolonger effective because of resistance of the fungus, or cannot be usedfor other reasons.

General Uses and Applications

The active agents or their mixtures are preferably applied in the formof compositions such as powders, dusting agents, granulates, solutions,emulsions or suspensions. Liquid and/or solid carrier materials, forinstance diluents and, if desired, cross-linking agents, adherentspromoting agents, emulsifiers and/or dispersants may be added.

Suitable liquid carrier materials are for instance water, aliphatic andaromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone,isophorone, dimethylsulfoxyide, dimethylformamide and furthermoremineral oil fractions.

As solid carrier materials there are suited mineral earths, for instancetonsil, silica gel, talc, kaolin, attaclay, limestone, silicic acid andvegetable products such as flours.

There may also be added surface active agents as for instancecalciumlignosulfonate, polyoxyethylenealkylphenyl-ether,naphthalenesulfone acids and their salts, phenolsulfone acids and theirsalt, formaldehyde condensation products, fatty alcohol sulfates andfurthermore substituted benzosulfone acids and their salts. If theactive agents are used for the pretreatment of the seed material, it isalso possible to add dyestuffs in order to give the pretreated seedmaterial a distinct color.

The ratio of the active agent or agents in the different compositionscan be varied over a broad range. The compositions, for instance, maycontain about 10 to 80% by weight of active agents, about 90 to 20% byweight of liquid or solid carrier materials and, if desired, up to 20%by weight of surface active agent in which case case a correspondingreduction of the carrier material takes place.

The application of the compositions can be effected in conventionalmanner, for instance with water as carrier material in spray amounts ofabout 100 to 1000 liter per about 2.5 acres. An application of thecomposition is possible in the so-called "low volume" or"ultra-low-volume process" as also in the form of so-called microgranulates.

Process of Making

The compounds which to the applicants' knowledge have not been describedso far in the literature can be made by way of different processes.

A. 1,2,3-triazoles of the formula ##STR3## are reacted with carbamoylhalides of the formula ##STR4## in the presence of acid acceptors orthey are reacted with isocyanates of the formula

    R.sub.3 --N═C═O                                    IV

if desired, in the presence of a catalyst, preferably an organic baseas, for instance, triethylamine.

B. Metal compounds of the formula ##STR5## may be reacted withcarbamoylhalides of the formula ##STR6## or with isocyanates of theformula

    R.sub.3 --N═C═O                                    IV

C. 1,2,3-triazole carboxylic acid halides of the formula ##STR7## may bereacted with amines of the formula ##STR8## in the presence of acidacceptors. D. Carbonylbis-1,2,3-triazoles of the formula ##STR9## may bereacted with amines of the formula ##STR10##

In all these formulas wherever used R₁, R₂, R₃, R₄ and n have the samemeaning as in the above-given formula I, and X is a halogen, preferablya chlorine atom and B is a univalent metal equivalent, preferably asodium, potassium or lithium atom.

The reaction of the components takes place between 0° and 120° C.,generally at room temperature. The components are used in aboutequimolar amounts. As reaction media there may be used polar organicsolvents. The selection of the solvents or suspension agents depends onthe kind of carbamoyl halides, of the kind of acid acceptors, on themetal compounds and the corresponding isocyanates used in the reaction.

As solvents or suspension agents there may, for instance be mentioned:acid nitriles, such as acetonitrile; ether, such as tetrahydrofuran anddioxane; acid amides, such as dimethylformamide; ketones, such asacetone; or chlorinated hydrocarbons, such as chloroform andtetracarbonchloride.

As acid acceptors there are suitable organic bases, for instancetriethylamine, N,N-dimethylamine and pyridine or inorganic bases such asoxides, hydroxides and carbonates of the alkali earth- and alkalimetals. Liquid bases such as pyridine and the use simultaneously as thesolvents.

The 1,2,3-triazolcarboxylic acid amides made by the described processeswhich are liquids or solids may be isolated from a reaction mixture inconventional form, for instance by distilling off the solvent employedat atmospheric or reduced pressure or by precipitation with water.

Although the compounds of the invention in these processes are obtainedin a highly pure form they can further be purified if desired forinstance by recrystallization or by chromatography.

Starting Products

The 1,2,3-triazolecarboxylic acid halides which are used as startingproducts and have the formula ##STR11## can be obtained from thetriazoles of the above-given formula II by reaction with acarbonylhalide COX₂, preferably phosgene in conventional manner.

The carbonylbis-1,2,3-triazole which are used as starting products andhave the formula ##STR12## can be obtained by reacting 1 mole of atriazole of the above-given formula II with about 0.5 moles of acarbonylhalogenide COX₂, preferably phosgene in conventional form. Thereaction is preferably carried out in the presence of a suitable acidacceptor, for instance pyridine.

After forming the carbonylbis-1,2,3-triazole it is frequently preferablyto react this product without isolating it with an amine of the formula##STR13##

The other starting products are known or can be made by obvious priorart processes. For instance, the 1,2,3-triazoles of the formula II canbe obtained by alkylating the corresponding 4-mercapto triazoles andthen subjecting the reaction product preferably according to knownprocedures to a step-by-step oxidation.

The following examples will further illustrate the making of thestarting products.

(A) Alkylthio-1,2,3-triazoles: 4-methyl-5-methylthio-1,2,3-triazole ofthe formula ##STR14##

4.79 g (0.12 mole) of sodium hydroxide dissolved in 20 ml ethanol areadded dropwise to a solution of 13.8 (0.12 mole) of5-mercapto-4-methyl-1,2,3-triazole in 60 ml ethanol. The addition iscarried out at room temperature and the sodium hydroxide is applied assolution in 20 ml ethanol. Thereupon a reaction is effected at 30° C.with 19.85 g (0.14 mole) methyliodide and the reaction product afterpermitting to stand overnight at room temperature is then subjected toconcentration in a vacuum at 40° C.

The residue is reacted with 150 ml water and is extracted with ether.The organic phase is dried on magnesium sulfate, filtrated andconcentrated. The remaining crystals are recrystallized fromcyclohexane.

The yield is 14.6 g=94.3% of the theoretical amount.

m.p.: 71°-71.5° C.

C₄ H₇ N₃ S: molecular weight 129.19.

The following starting products were made in an analogous manner:

    ______________________________________                                                                Physical                                              Name                    Constants                                             ______________________________________                                        4-methylthio-1,2,3-triazole                                                                           m.p.: 47° C.                                   4-ethylthio-1,2,3-triazole                                                                            n.sub.D.sup.20 : 1.5449                               4-propylthio-1,2,3-triazole                                                                           n.sub.D.sup.20 : 1.5375                               4-isopropylthio-1,2,3-triazole                                                                        n.sub.D.sup.20 : 1.5331                               4-butylthio-1,2,3-triazole                                                                            n.sub.D.sup.20 : 1.5280                               4-(1-methylpropylthio)-1,2,3-triazole                                                                 n.sub.D.sup.20 : 1.5281                               4-allylthio-1,2,3-triazole                                                                            n.sub.D.sup.20 : 1.5561                               4-isobutylthio-1,2,3-triazole                                                                         n.sub.D.sup.20 : 1.5244                               4-(2-propinylthio)-1,2,3-triazole                                                                     semicrystals                                          4-benzylthio-1,2,3-triazole                                                                           m.p.: 61.5° -                                                            63.5° C.                                     ______________________________________                                    

(B) Alkylsulfinyl-1,2,3-triazoles: 4-methylsulfinyl-1,2,3-triazole##STR15##

A solution of 57.5 g (0.5 mole) of 4-methylthio-1,2,3-triazole in 200 mlacetic acid is added dropwise within 10 minutes to 61.1 ml (0.6 mole)30% hydrogen perioxide. The solution is then stirred for 30 minutes at atemperature of 40°-45° C. After standing overnight it is heated furtherfor 30 minutes to 80° C., then cooled to room temperature whereupon thedark red reaction solution is decolorized with 0.2 g of sodiumdisulfite. The reaction solution is then concentrated in a vacuum at 40°C.The oily residue is recrystallized by digestion with diisopropylether.

Yield: 62.3 g=95% of the theoretical value

m.p.: 66°-67° C.

C₃ H₅ N₃ OS: molecular weight 131.16.

(C) Alkylsulfonyl-1,2,3-triazoles: 4-propylsulfonyl-1,2,3-triazole##STR16##

170.5 g (1.08 mole) of sodium permangamate are added batchwise within aperiod of 30 minutes at 45° to 55° C. to a solution of 103.2 g (0.72mole) of 4-propylthio-1,2,3-triazole in 320 ml acetic acid and 420 mlwater. The solution is then stirred for 10 minutes at 45° C. and reactedat 20° C. with a solution of 159.8 g (0.84 mole) of sodium disulfite in500 ml water up to complete decolorization. Thereupon extraction iseffected four times with 250 ml of acetic acid ester. The organic phaseis then dried on magnesium sulfate, filtered and concentrated in avacuum.

Yield: 119 g=94.5% of the theoretical value

n_(D) ²⁰ : 1.5085

C₅ H₉ N₃ O₂ S: molecular weight 175.21.

The following starting products have been made in analogous manner:

    ______________________________________                                                               Physical                                               Name                   Constants                                              ______________________________________                                        4-methylsulfonyl-1,2,3-triazole                                                                      m.p.: 101°-103° C.                       4-isopropylsulfonyl-1,2,3-triazole                                                                   n.sub.D.sup.20 : 1.5067                                4-benzylsulfonyl-1,2,3-triazole                                                                      m.p.: 163°-166° C.                       4-ethylsulfonyl-1,2,3-triazole                                                                       m.p.: 46°-48° C.                         4-butylsulfonyl-1,2,3-triazole                                                                       n.sub.D.sup.20 : 1.4948                                4-(1-methylpropylsulfonyl)-1,2,3-triazole                                                            n.sub.D.sup.20 : 1.4858                                4-isobutylsulfonyl-1,2,3-triazole                                                                    m.p.: 71°-73° C.                         ______________________________________                                    

EXAMPLES OF THE COMPOUNDS OF THE INVENTION

The following Examples will illustrate the making of the 1,2,3-triazolecarboxylic acid amides.

EXAMPLE 1 4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acidpropylamide (Compound No. 1)

8.75 g (0.05 mole) of 4-propylsulfonyl-1,2,3-triazole dissolved in 75 mlacetonitrile were reacted at room temperature with 5.55 g (0.055 mole)triethylamine. Upon stirring 8.18 g (0.05 mole) ofdipropylcarbamoylchloride were then added at 70° C. within a period of10 minutes. The solution was then further stirred for 2 hours at 70° C.and permitted to stand overnight. It was then concentrated in a vacuo at40° C. The residue was reacted with 100 ml ice water and extracted withether. The organic phase was thereafter washed with a 1% sodiumbicarbanate solution, dried on magnesium sulfate, filtered andconcentrated.

Yield: 12.6 g=18.4% of the theoretical value

n_(D) ²⁰ : 1.4964.

Probably the product is an isomer mixture of N¹ and N² -carbamoylproducts.

EXAMPLE 2 4-methyl-5-methylthio-1,2,3-triazole-1(2,3)-carboxylic aciddimethylamide (Compound no. 2) ##STR17##

16.4 g (0.127 mole) of 4-methyl-5-methylthio-1,2,3-triazole, dissolvedin 160 ml of tetrahydrofuran were reacted at room temperature with 15.35g (0.152 mole) of triethylamine. Thereafter 16.3 g (0.152 mole) ofdimethylcarbamoylchloride were added within a period of 5 minutes uponstirring at a temperature of 50° C. Stirring was then continued for 4hours at 50° C. and the reaction product was permitted to stand for 1day at room temperature. It was then concentrated in a vacuum at 40° C.The residue was reacted at 150 ml water and was twice extracted with 75ml, each, of chloroform. The organic phase was then washed with a 1%sodium bicarbonate solution, dried on magnesium sulfate, filtered andconcentrated.

Yield: 23.5 g=92.5% of the theoretical value

n_(D) ²⁰ : 1.5370.

The product is a uniform isomer probably a N² -carbamoyl product.

EXAMPLE 3 4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid methylamide(Compound No. 3) ##STR18##

11.5 g (0.1 mol) of 4-methylthio-1,2,3-triazole were dissolved in 100 mlof tetrahydrofuran and then reacted with 6.27 g (0.11 mole) ofmethylisocyanate within a period of 3 minutes at 5° C. There werefurthermore added as catalyst 0.1 ml of triethylamine. Subsequently,stirring was continued for 1 hour at 5° C. and then for another 11/2hour at room temperature. Concentration was then effected in a vacuumand 40° C. and the resulting residue (an isomer mixture) wasrecrystallized upon vigorous stirring from 500 ml water.

Yield: 8.7 g=50.5% of the theoretical value

m.p.: 107°-109° C. (decomposition).

The product is uniform isomer probably an N² carbamoyl product.

EXAMPLE 4 4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid methylamide(Compound No. 4) ##STR19##

11.5 g (0.1 mole) of 4-methylthio-1,2,3-triazole were dissolved in 125ml carbon tetrachloride and were then reacted with 6.27 g (0.11 mole) ofmethylisocyanate at room temperature within a period of 10 minutes.After standing overnight the crystals were removed by suction andfurther washed with a little carbontetrachloride. The crystals were thenrecrystallized from benzene/cyclohexane.

Yield: 12.2 g=70.9% of the theoretical value

m.p.: 109°-110° C. (decomposition)

The product is a uniform isomer, probably and N¹ carbamoyl product.

The further compounds of the invention were made in an analogous manner.

    ______________________________________                                        Com-                                                                          pound                       Physical                                          No.   Name                  Constants                                         ______________________________________                                        5     4-methylthio-1,2,3-triazole                                                   1(2,3)-carboxylic acid methyl-                                                                      m.p.: 93° C.                                     amide (isomer mixture)                                                                              (decomposed)                                      6     4-methylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid anilide                                                                      m.p.: 86.5°-89° C.                        (isomer mixture)      (decomposed)                                      7     4-methylthio-1,2,3-triazole                                                   1(2,3)-carboxylic acid ethyl-                                                                       semicrystalline                                         amide (isomer mixture)                                                  8     4-methylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid propyl-                                                                      n.sub.D.sup.20 = 1.5482                                 amide (isomer mixture)                                                  9     4-methylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid butyl-                                                                       n.sub.D.sup.20 = 1.5400                                 amide (isomer mixture)                                                  10    4-methylthio-1,2,3-thiazole-                                                  1(2,3)-carboxylic acid cyclo-                                                                       m.p.: 63°-71° C.                          hexylamide (isomer mixture)                                             11    4-methylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid anilide                                                                      m.p.: 98°-100° C.                         (N.sup.I - isomer)                                                      12    4-methylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid anilide                                                                      m.p.: 93°-95° C.                          (N.sup.2 - isomer)                                                      13    4-methylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid-(2-methyl-                                             anilide) (N.sup.2 - isomer)                                                                         m.p.: 80°-88° C.                    14    4-methylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic-acid-(2-                                                                          m.p.: 110° C.                                    chloroanilide) (N.sup.2 - isomer)                                                                   (decomposed)                                      15    4-methylthio-1,2,3-triazole                                                   1(2,3)-carboxylic acid-(3-                                                                          m.p.: 91°-92.5° C.                        methylanilide) (N.sup.1 - isomer)                                                                   (decomposed)                                      16    4-methylthio-1,2,3-triazole                                                   1(2,3)-carboxylic acid-(4-                                                                          m.p.: 108.5°-                                    methylanilide) (N.sup.1 - isomer)                                                                   109.5° C.                                                              (decomposed)                                      17    4-methylthio-1,2,3-triazole                                                   1(2,3)-carboxylic acid-(3-chloro-                                                                   m.p.: 106°-107° C.                        anilide) (N.sup.1 - isomer)                                                                         (decomposed)                                      18    4-methylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid-(4-                                                                          m.p.: 109°-110° C.                        chloroanilide) (N.sup.1 - isomer)                                                                   (decomposed)                                      19    4-methylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid allyl-                                                                       m.p.: 50°-55° C.                          amide (N.sup.1 - isomer)                                                20    4-methylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid dimethyl-                                                                    n.sub.D.sup.20 : 1.5569                                 amide (isomer mixture)                                                  21    4-ethylthio-1,2,3-triazole-                                                   1(2,3)-carboxylic acid methyl-                                                                      n.sub.D.sup.20 : 1.5571                                 amide (isomer mixture)                                                  22    4-propylthio-1,2,3-triazole                                                   1(2,3)-carboxylic acid methyl-                                                                      m.p.: 35°-38° C.                          amide (isomer mixture)                                                  23    4-isopropylthio-1,2,3-triazole-                                               1(2,3)-carboxylic acid methyl-                                                                      n.sub.D.sup.20 : 1.5432                                 amide (isomer mixture)                                                  24    4-butylthio-1,2,3-triazole                                                    1(2,3)-carboxylic acid methyl                                                                       n.sub.D.sup.20 : 1.5408                                 amide (isomer mixture)                                                  25    4-(1-methylpropylthio)-1,2,3-                                                 trizole-1(2,3)-carboxylic acid-                                                                     n.sub.D.sup.20 : 1.5390                                 methylamide (isomer mixture)                                            26    4-allylthio-1,2,3-triazole-                                                   1(2,3)-carboxylic acid methyl-                                                                      semicrystal                                             amide (isomer mixture)                                                  27    4-butylthio-1,2,3-triazole-                                                   1(2,3)-carboxylic acid methyl-                                                                      m.p.: 75°-77° C.                          amide (N.sup.1 - isomer)                                                28    4-(1-methylpropylthio)-                                                       1,2,3-triazole-1(2,3)-carboxylic                                              acid methylamide (N.sup.1 - isomer)                                                                 m.p.: 66°-69° C.                    29    4-allylthio-1,2,3-triazole-                                                   1(2,3)-carboxylic acid methyl-                                                                      m.p.: 84°-85° C.                          amide (N.sup.1 - isomer)                                                30    4-ethylthio-1,2,3-triazole-                                                   1(2,3)-carboxylic acid methyl-                                                                      m.p.: 84.5°-86° C.                        amide (N.sup.1 - isomer)                                                31    4-propylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid methyl-                                                                      m.p.: 75°-78° C.                          amide (N.sup.1 - isomer)                                                32    4-isopropylthio-1,2,3-triazole-                                               1(2,3)-carboxylic acid methyl-                                                                      m.p.: 91°-92.5° C.                        amide (N.sup.1 - isomer)                                                33    4-isobutylthio-1,2,3-triazole-                                                1(2,3)-carboxylic acid methyl-                                                                      n.sub.D.sup.20 : 1.5382                                 amide (isomer mixture)                                                  34    4-(2-propinylthio)-1,2,3-                                                     triazole-1(2,3)-carboxylic acid                                                                     semicrystal                                             methylamide) (isomer mixture)                                           35    4-benzylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid methyl-                                                                      m.p.: 50°-54° C.                          amide (isomer mixture)                                                  36    4-isobutylthio-1,2,3-triazole-                                                1(2,3)-carboxylic acid methyl-                                                                      m.p.: 82°-83.5° C.                        amide (N.sup.1 - isomer)                                                37    4-(2-propinylthio)-1,2,3-                                                     triazole-1(2,3)-carboxylic                                                                          m.p.: 101°-102° C.                        acid methylamide (N.sup.1 - isomer)                                     38    4-benzylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid methyl-                                                                      m.p.: 84°-85° C.                          amide (N.sup.1 - isomer)                                                39    4-methylsulfonyl-1,2,3-tria-                                                  zol-1(2,3)-carboxylic acid di-                                                methylamide (isomer mixture)                                                                        m.p.: 73°- 83° C.                   40    4-methylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid methyl-                                                amide (isomer mixture)                                                                              m.p.: 132°-134° C.                  41    4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                                          m.p.: 110°-111° C.                        acid ethylamide (isomer mixture)                                        42    4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid propylamide (isomer                                                                            m.p.: 66°-72° C.                          mixture)                                                                43    4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid butylamide (isomer                                                                             m.p.: 70°-72° C.                          mixture)                                                                44    4-methylsulfinyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid methylamide (isomer                                                                            m.p.: 95°-97° C.                          mixture)                                                                45    4-methylsulfinyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid ethylamide       n.sub.D.sup.20 : 1.5370                                 (isomer mixture)                                                        46    4-methylsulfinyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid propylamide      n.sub.D.sup.20 : 1.5288                                 (isomer mixture)                                                        47    4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid anilide          m.p.: 134°-137° C.                        (isomer mixture)                                                        48    4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid cyclohexylamide  m.p.: 96°-103° C.                         (isomer mixture)                                                        49    4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid (4-chloroanilide)                                                                              m.p.: 170°-171° C.                        (isomer mixture)                                                        50    4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid (4-methylanilide)                                                                              m.p.: 156°-158° C.                        (isomer mixture)                                                        51    4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid allylamide       m.p.: 91°-92.5° C.                        (isomer mixture)                                                        52    4-methyl-5-methylthio-                                                        triazole-1(2,3)-carboxylic                                                    acid methylamide      m.p.: 102°-106° C.                        (N.sup.2 - isomer)                                                      53    4-methylsulfinyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid butylamide       n.sub.D.sup.20 : 1.5128                                 (isomer mixture)                                                        54    4-methylsulfinyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid (4-methylanilide)                                                                              m.p.: 122°-123° C.                        (isomer mixture)                                                        55    4-methylsulfinyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid (4-chloroanilide)                                                                              m.p.: 150° C.                                    (isomer mixture)      (decomposed)                                      56    4-methylsulfinyl-1,2,3-                                                       triazol-1(2,3)-carboxylic                                                     acid allylamide       n.sub.D.sup.20 : 1.5365                                 (isomer mixture)                                                        57    4-methylsulfinyl-1,2,3-                                                       triazol-1(2,3)-carboxylic                                                     acid dimethylamide    n.sub.D.sup.20 : 1.5391                                 (isomer mixture)                                                        58    4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid diethylamide     n.sub.D.sup.20 : 1.5065                                 (isomer mixture)                                                        59    4-ispropylsulfonyl-1,2,3-                                                     triazole-1(2,3)-carboxylic                                                    acid methylamide      m.p.: 141°-149° C.                        (isomer mixture)                                                        60    4-isopropylsulfonyl-1,2,3-                                                    triazole-1(2,3)-carboxylic                                                    acid dimethylamide    m.p.: 112°-113° C.                        (N.sup.1 - isomer)                                                      61    4-isopropylsulfonyl-1,2,3-                                                    triazole-1(2,3)-carboxylic                                                    acid dimethylamide    n.sub.D.sup.20 : 1.5061                                 (N.sup.2 - isomer)                                                      62    4-isopropylsulfonyl-1,2,3-                                                    triazole-1(2,3)-carboxylic                                                    acid diethylamide     n.sub.D.sup.20 : 1.4909                                 (isomer mixture)                                                        63    4-propylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid methylamide      m.p.: 99°-109° C.                         (isomer mixture)                                                        64    4-propylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid dimethylamide    n.sub.D.sup.20 : 1.5131                                 (isomer mixture)                                                        65    4-propylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid diethylamide     n.sub.D.sup.20 : 1.4992                                 (isomer mixture)                                                        66    4-propylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid ethylamide       m.p.: 48°-60° C.                          (isomer mixture)                                                        67    4-propylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid (N-ethyl-N-propyl)-amide                                                                       n.sub.D.sup.20 : 1.5031                                 (isomer mixture)                                                        68    4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid (N-ethyl-N-propyl)-amide                                                                       n.sub.D.sup.20 : 1.5081                                 (isomer mixture)                                                        69    4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid-N-ethylanilide   n.sub.D.sup.20 : 1.5489                                 (isomer mixture)                                                        70    4-isopropylsulfonyl-1,2,3-                                                    triazole-1(2,3)-carboxylic acid                                               N-ethylanilide        n.sub.D.sup.20 : 1.5384                                 (isomer mixture)                                                        71    4-propylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid N-ethylanilide   n.sub.D.sup.20 : 1.5406                                 (isomer mixture)                                                        72    4-isopropylsulfonyl-1,2,3-                                                    triazole-1(2,3)-carboxylic                                                    acid (N-ethyl-N-propyl)-amide                                                                       n.sub.D.sup.20 : 1.5028                                 (isomer mixture)                                                        73    4-isobutylthio-1,2,3-triazole-                                                1(2,3)-carboxylic acid di-                                                                          n.sub.D.sup.20 : 1.5439                                 methylamide (isomer mixture)                                            74    4-isobutylthio-1,2,3-triazole-                                                1(2,3)-carboxylic acid dimethyl-                                                                    n.sub.D.sup.20 : 1.5321                                 amide(isomer mixture)                                                   75    4-butylsulfonyl-1,2,3-triazole-                                               1(2,3)-carboxylic acid dimethyl-                                              amide (isomer mixture)                                                                              n.sub.D.sup.20 : 1,5119                           76    4-butylsulfonyl-1,2,3-triazole-                                               1(2,3)-carboxylic acid diethyl-                                               amide (isomer mixture)                                                                              n.sub.D.sup.20 : 1,5010                           77    4-isobutylsulfonyl-1,2,3-                                                     triazole-1(2,3)-carboxylic                                                    acid dimethylamide (isomer mix-                                               ture)                 n.sub.D.sup.20 : 1,5107                           78    4-isobutylsulfonyl-1,2,3-                                                     triazole-1(2,3)-carboxylic                                                    acid diethylamide     n.sub.D.sup.20 : 1,4999                                 isomer mixture)                                                         79    4-ethylsulfonyl-1,2,3-triazole-                                               1(2,3)-carboxylic acid dimethyl-                                              amide (isomer mixture)                                                                              m.p.: 79°-82° C.                    80    4-ethylsulfonyl-1,2,3-triazole-                                               1(2,3)-carboxylic acid diethyl-                                               amide (isomer mixture)                                                                              n.sub.D.sup.20 : 1,5080                           81    4-(1-methylpropylsulfonyl)-                                                   1,2,3-triazole-1(2,3)-carboxy-                                                lic acid dimethylamide                                                                              n.sub.D.sup.20 : 1,5110                                 (isomer mixture)                                                        82    4-benzylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid diethylamide     m.p.: 90°-91° C.                          (isomer mixture)                                                        83    4-butylthio-1,2,3-triazole-                                                   1(2,3)-carboxylic acid di-                                                    ethylamide (isomer mixture)                                                                         n.sub.D.sup.20 : 1,5242                           84    4-(1-methylpropylsulfonyl)-                                                   1,2,3-triazole-1(2,3)-carboxy-                                                lic acid diethylamide n.sub.D.sup.20 : 1,5419                                 (isomer mixture)                                                        85    4-benzylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid dimethyl-                                              amide (isomer mixture)                                                                              n.sub.D.sup.20 : 1,5538                           86    4-ethylthio-1,2,3-triazole-1                                                  (2,3)-carboxylic acid dimethyl-                                               amide (isomer mixture)                                                                              n.sub.D.sup.20 : 1,5458                           87    4-ethylthio-1,2,3-triazole-1                                                  (2,3)-carboxylic acid diethyl-                                                amide (isomer mixture)                                                                              n.sub.D.sup.20 : 1,5351                           88    4-isobutylthio-1,2,3-triazole-                                                1(2,3)-carboxylic acid diethyl-                                               amide (isomer mixture)                                                                              n.sub.D.sup.20 : 1,5210                           89    4-(1-methylpropylthio)-1,2,3-                                                 triazole-1(2,3)-carboxylic                                                    acid dimethylamide    n.sub.D.sup.20 : 1,5331                                 (isomer mixture)                                                        90    4-(1-methylpropylthio)-1,2,3-                                                 triazole-1(2,3)-carboxylic acid                                                                     n.sub.D.sup.20 : 1,5235                                 diethylamide (isomer mixture)                                           91    4-benzylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid dimethyl-                                                                    n.sub.D.sup.20 : 1,5988                                 amide (isomer mixture)                                                  92    4-benzylthio-1,2,3-triazole-                                                  1(2,3)-carboxylic acid diethyl-                                               amide (isomer mixture)                                                                              n.sub.D.sup.20 : 1,5760                           93    4-4-propylsulfonyl-1,2,3-triazole-                                            1(2,3)-carboxylic acid propyl-                                                                      m.p.: 67°-69°  C.                         amide (isomer mixture)                                                  94    4-propylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic acid                                                                     m.p.: 76°-79° C.                          butylamide (isomer mixture)                                             95    4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid isopropyl-                                             amide (isomer mixture)                                                                              m.p.: 68°-72° C.                    96    4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid dibutyl-                                               amide (isomer mixture)                                                                              n.sub.D.sup.20 : 1,4909                           97    4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid pyrroli-                                               dide (isomer mixture) n.sub.D.sup.20 : 1,5305                           98    4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid piperi-                                                                      n.sub.D.sup.20 : 1,5270                                 dide (isomer mixture)                                                   99    4-propylsulfonyl-1,2,3-tria-                                                  zole-1(2,3)-carboxylic acid                                                                         n.sub.D.sup.20 : 1,5176                                 diallylamide (isomer mixture)                                           100   4-propylsulfonyl-1,2,3-tria-                                                  zole-1(2,3)-carboxylic acid                                                                         n.sub.D.sup.20 : 1,5251                                 morpholide (isomer mixture)                                             101   4-butylsulfonyl-1,2,3-tria-                                                   zole-1(2,3)-carboxylic acid                                                   (N-ethyl-N-propyl-amide                                                                             n.sub.D.sup.20 : 1,4990                                 (isomer mixture)                                                        102   4-isobutylsulfonyl-1,2,3-                                                     triazole-1(2,3)-carboxylic                                                    acid-(N-ethyl-N-propyl)-amide                                                                       n.sub.D.sup.20 : 1,4972                                 (isomer mixture)                                                        103   4-(1-methylpropylsulfonyl)-                                                   1,2,3-triazole-1(2,3)-carboxy-                                                lic acid-(N-ethyl-N-propyl)-                                                                        n.sub.D.sup.20 : 1,4990                                 amide (isomer mixture)                                                  104   4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid-N-ethyl-                                                                     N.sub.D.sup.20 : 1,4971                                 N-butyl)amide (isomer mixture)                                          105   4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid dipentyl-                                                                    n.sub.D.sup.20 : 1,4880                                 amide (isomer mixture)                                                  106   4-propylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid-N-ethyl-N-cyclohexyl)-                                                                         n.sub.D.sup.20 : 1,5161                                 amide (isomer mixture)                                                  107   4-propylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid diisopropylamide n.sub.D.sup.20 : 1,5010                                 (isomer mixture)                                                        108   4-ethylsulfonyl-1,2,3-                                                        triazole-1(2,3)-carboxylic                                                    acid-N-ethyl-N-propyl)-amide                                                                        n.sub.D.sup.20 : 1,4998                                 (isomer mixture)                                                        109   4-ethylsulfonyl-1,2,3-                                                        triazole-1(2,3)-carboxylic                                                    acid dipropylamide    m.p.: 60°-61° C.                          (isomer mixture)                                                        110   4-ethylsulfonyl-1,2,3-triazole-                                               1(2,3)-carboxylic acid dibutyl-                                               amide (isomer mixture)                                                                              n.sub.D.sup.20 : 1,4931                           111   4-butylsulfonyl-1,2,3-                                                        triazole-1(2,3)-carboxylic                                                    acid dipropylamide    n.sub.D.sup.20 : 1,4949                                 (isomer mixture)                                                        112   4-butylsulfonyl-1,2,3-                                                        triazole-1(2,3)-carboxylic                                                    acid dibutylamide     n.sub.D.sup.20 : 1,4900                                 (isomer mixture)                                                        113   4-(1-methylpropylsulfonyl)                                                    1,2,3-triazole-1(2,3)-car-                                                    boxylic acid dibutylamide                                                                           n.sub.D.sup.20 : 1,4910                                 (isomer mixture)                                                        114   4-isobutylsulfonyl-1,2,3-                                                     triazole-1(2,3)-carboxylic                                                    acid dipropylamide    n.sub.D.sup.20 : 1,4920                                 (isomer mixture)                                                        115   4-isobutylsulfonyl-1,2,3-                                                     triazole-1(2,3)-carboxylic                                                    acid dibutylamide     n.sub.D.sup.20 : 1,4887                                 (isomer mixture)                                                        116   4-(1-methylpropyl)-sulfonyl-                                                  1,2,3-triazole-1(2,3)-carbox-                                                 ylic acid dipropylamide                                                                             n.sub.D.sup.20 : 1,4946                                 (isomer mixture)                                                        117   4-(1-methylpropyl)-sulfonyl-                                                  1,2,3-triazole-1(2,3)-carboxylic                                              acid diisopropylamide n.sub.D.sup.20 : 1,4971                                 (isomer mixture)                                                        118   4-butylsulfonyl-1,2,3-triazole-                                               1(2,3)-carboxylic acid-(N-ethyl-                                                                    N.sub.D.sup.20 : 1,4951                                 (isomer mixture)                                                        119   4-isobutylsulfonyl-1,2,3-tria-                                                zole-1(2,3)-carboxylic acid                                                   (N-ethyl-N-butyl)-amide                                                                             n.sub.D.sup.20 : 1,4943                                 (isomer mixture)                                                        120   4-(1-methylpropyl)-sulfonyl-                                                  1,2,3-triazole-1(2,3)-carboxylic                                              acid-(N-ethyl-N-butyl)-amide                                                                        n.sub.D.sup.20 : 1,4968                                 (isomer mixture)                                                        121   4-ethylsulfonyl-1,2,3-triazole-                                               1(2,3)-carboxylic acid-(N-ethyl-                                              N-cyclohexyl)-amide   n.sub.D.sup.20 : 1,5160                           122   4-isopropylsulfonyl-1,2,3-                                                    triazole-1(2,3)-carboxylic                                                    acid dipropylamide    m.p.: 58°-60° C.                          (isomer mixture)                                                        124   4-butylsulfonyl-1,2,3-                                                        triazole-1(2,3)-carboxylic acid                                               (N-ethyl-N-cyclohexyl)-amide                                                                        n.sub.D.sup.20 : 1,5111                                 (isomer mixture)                                                        125   4-(1-methylpropyl)-sulfonyl-                                                  1,2,3-triazole-1(2,3)-carboxylic                                              acid-(N-ethyl-N-cyclohexyl)amide                                              (isomer mixture)      n.sub.D.sup.20 : 1,5100                           126   4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid diiso-                                                                       n.sub.D.sup.20 : 1,5011                                 butylamide (isomer mixture)                                             127   4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid dihexyl-                                                                     n.sub.D.sup.20 : 1,4891                                 amide (isomer mixture)                                                  128   4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid-(N-ethyl-                                                                    n.sub.D.sup.20 : 1,5444                                 N-benzyl)-amide (isomer mixture)                                        129   4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid-(N-                                                    ethyl-N-isopropyl)-amide (isomer                                              mixture)                                                                130   4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid-N,N-hexa-                                                                    n.sub.D.sup.20 : 1,5272                                 methyleneamide (isomer mixture)                                         131   4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid-N-(2-cyano-                                            ethyl)-anilide (isomer mixture)                                                                     m.p.: 124° C.                              132   4-propylsulfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid-N-methyl-                                              anilide (isomer mixture)                                                133   4-ethylsulfonyl-1,2,3-triazole-                                               1(2,3)-carboxylic acid-(N-ethyl-                                                                    n.sub.D.sup.20 : 1,5002                                 N-butyl)-amide (isomer mixture)                                         134   4-isopropylfonyl-1,2,3-triazole-                                              1(2,3)-carboxylic acid-(N-ethyl-                                                                    deliquescent                                            N-butyl)-amide (isomer mixture)                                         135   4-isobutylsulfonyl-1,2,3-                                                     triazole-1(2,3)-carboxylic                                                    acid-(N-ethyl-N-cyclohexyl)-                                                                        n.sub.D.sup.20 : 1,5078                                 amide (isomer mixture)                                                  136   4-butylsulfonyl-1,2,3-triazole-                                               1(2,3)-carboxylic acid-(N-ethyl-                                              N-isopropyl)-amide (isomer                                                                          n.sub.D.sup.20 : 1,4962                                 mixture)                                                                137   4-isobutylsulfonyl-1,2,3-                                                     triazole-1(2,3)-carboxylic                                                    acid-(N-ethyl-N-isopropyl)-amide                                              (isomer mixture)      n.sub.D.sup.20 : 1,4970                           138   4-propylsulfinyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid diethylamide     n.sub.D.sup.20 : 1,5192                                 (isomer mixture)                                                        139   4-propylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid-bis(2-chloroethyl)amide                                                                        n.sub.D.sup.20 : 1,5238                                 (isomer mixture)                                                        140   4-butylsulfonyl-1,2,3-                                                        triazole-1(2,3)-carboxylic                                                    acid-(N-ethyl-N-benzyl)-                                                                            n.sub.D.sup.20 : 1,5429                                 amide (isomer mixture)                                                  141   4-(1-methylpropyl)-sulfonyl-                                                  1,2,3-triazole-1(2,3)-carboxy-                                                lic acid-(N-ethyl-N-benzyl)-                                                                        n.sub.D.sup.20 : 1,5392                                 amide (isomer mixture)                                                  142   4-isobutylsulfonyl-1,2,3-                                                     triazole-1(2,3)-carboxylic                                                    acid-(N-ethyl-N-benzyl)-amide                                                                       n.sub.D.sup.20 : 1,5361                                 (isomer mixture)                                                        143   4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid-(N-ethyl-N-butyl)-amide                                                                        m.p.: 60°-62° C.                          (isomer mixture)                                                        144   4-ethylthio-5-methyl-1,2,3-                                                   triazole-1(2,3)-carboxylic acid-                                              (dimethyl)-amide (isomer                                                                            n.sub.D.sup.20 : 1,5333                                 (mixture)                                                               145   4-propylsulfonyl-5-methyl-                                                    1,2,3-triazole-1(2,3)-car-                                                    boxylic acid-dipropylamide                                                                          n.sub.D.sup.20 : 1,4967                                 (isomer mixture)                                                        146   4-propylsulfonyl-5-methyl-                                                    1,2,3-triazole-1(2,3)-carboxy-                                                lic acid-(N-ethyl-N-isopropyl)-                                                                     n.sub.D.sup.20 : 1,4967                                 amide (isomer mixture)                                                  147   4-(2-propinylthio-5-methyl-                                                   1,2,3-triazole-1(2,3)-carboxy-                                                lic acid-dimethylamide                                                                              n.sub.D.sup.20 : 1,5568                                 (isomer mixture)                                                        148   4-methylsulfonyl-1,2,3-                                                       triazole-1(2,3)-carboxylic                                                    acid-(N-ethyl-N-isopropyl)-                                                   amide (isomer mixture)                                                                              n.sub.D.sup.20 : 1,4989                           149   4-ethylsulfonyl-1,2,3-triazole-                                               1(2,3)-carboxylic acid-(N-ethyl-                                              N-isopropyl)-amide    n.sub.D.sup.20 : 1,5000                                 (isomer mixture)                                                        150   4-(1-methyl-propyl)-sulfonyl-                                                 1,2,3-triazole-1(2,3)-carboxy-                                                lic acid-(N-ethyl-N-isopropyl)-                                                                     n.sub.D.sup.20 : 1,4959                                 amide (isomer mixture)                                                  151   4-ethylsulfonyl-1,2,3-triazole-                                               1(2,3)-carboxylic acid-diiso-                                                 propylamide (isomer mixture)                                                                        n.sub.D.sup.20 : 1,4952                           152   4-isobutylsulfonyl-1,2,3-                                                     triazole-1(2,3)-carboxylic                                                    acid-diisopropylamide n.sub.D.sup.20 : 1,4925                                 (isomer mixture)                                                        153   4-butylsulfonyl-1,2,3-                                                        triazole-1(2,3)-carboxylic                                                    acid diisopropylamide n.sub.D.sup.20 : 1,4935                                 (isomer mixture)                                                        154   5-methyl-4-propylsulfonyl-                                                    1,2,3-triazole-1(2,3)-carboxy-                                                lic acid diisopropylamide                                                                           n.sub.D.sup.20 : 1,4911                                 (isomer mixture)                                                        155   4-isopropylthio-5-methyl-                                                     1,2,3-triazole-1(2,3)-carboxy-                                                lic acid dimethylamide                                                                              n.sub.D.sup.20 : 1,5254                                 (isomer mixture)                                                        156   4-allylthio-5-methyl-1,2,3-                                                   carboxylic acid dimethylamide                                                                       n.sub.D.sup.20 : 1,5439                                 (isomer mixture)                                                        157   4-(2-cyanoethylthio)-5-                                                       methyl-1,2,3-triazole-1                                                       (2,3)-carboxylic acid di-                                                                           n.sub.D.sup.20 : 1,5400                                 methylamide (isomer mixture)                                            158   4-methylthio-5-propyl-1,2,3-                                                  triazole-1(2,3)-carboxylic                                                                          n.sub.D.sup.20 : 1,5292                                 acid-dimethylamide                                                      159   5-ethyl-4-methylthio-1,2,3-                                                   triazole-1(2,3)-carboxylic acid-                                                                    n.sub.d.sup.20 : 1,5370                                 dimethylamide                                                           160   5-isopropyl-4-methylthio-                                                     1,2,3-triazole-1(2,3)-carboxy-                                                                      n.sub.D.sup.20 : 1,5263                                 lic acid-dimethylamide                                                  161   5-tert.-butyl-4-methylthio-                                                   1,2,3-triazole-1(2,3)-carboxy-                                                                      n.sub.D.sup.20 : 1,5271                                 lic acid dimethylamide                                                  ______________________________________                                    

Physical Properties--Isomer Structure

The compounds of the invention are normally colorless and non-smellingoils or crystalline materials which have a moderate up to goodsolubility in aliphatic hydrocarbons, in halogenated hydrocarbons, suchas chloroform and carbon tetrachloride, ketones, such as acetone;carboxylic acid amides, such as dimethylformamide, sulfoxides, such asdimethylsulfoxide, carboxylic acid nitriles, such as acetonitrile andlower alcohols, such as methanol and ethanol. They have a limitedsolubility in water. The compounds of the invention as shown in formulaI may be present in the following isomeric structures: ##STR20## R₁, R₂,R₃, R₄ and n having the meaning as in formula I.

In the process of making there is possibly formed a mixture of the twoisomers A and B if R₂ is hydrogen.

Compounds which consist exclusively of the structure shown above is Aare possibly formed where R₂ is alkyl.

Since, however, the structure has not been completely clarified thecompounds of the invention within the framework of the presentspecification and claims are designated as1,2,3-triazole-1-(2,3)-carboxylic acid amides which is intended to meanthat there may be present any of the structures identified above as A, Bor C or an isomeric mixture thereof.

These mixtures could possibly be separated by conventional processes as,for instance, by a chromatographic procedure in which case thequantitative formation of one or the other isomer may be affected by theselection of a specific solvent. However, since the isomer mixtures havea particularly high biocidal activity the separation into individualisomers would be of no particular advantage.

Examples Illustrating Uses and Applications of the Compounds EXAMPLE 5

The compounds listed in the following Table I were applied in a hothouseby spraying in a preemergence application in amounts of 5 kg of activeagent per about 2.5 acres in an emulsion of 500 liters water toDigitaria s., Sorghum h, cotton and maize. Three weeks after treatmentthe results were evaluated on a scale from 0=to no action to 4=completedestruction of the plants.

As the table shows destruction of the weeds was accomplished while theagricultural plants were not damaged. The comparison compound contraryto these results destroyed also the agricultural plants.

                  TABLE I                                                         ______________________________________                                        Compound of the                 Digi- Sor-                                    Invention No.   maize   cotton  taria s.                                                                            ghum h.                                 ______________________________________                                        1               0       0       4     4                                       58              0       0       4     4                                       61              0       0       4     4                                       62              0       0       4     4                                       64              0       0       4     4                                       65              0       0       4     4                                       67              0       0       4     4                                       68              0       0       4     4                                       69              0       0       4     4                                       70              0       0       4     4                                       71              0       0       4     4                                       72              0       0       4     4                                       75              0       0       4     4                                       76              0       0       4     4                                       77              0       0       4     4                                       78              0       0       4     4                                       79              0       0       4     4                                       80              0       0       4     4                                       81              0       0       4     4                                       82              0       0       4     4                                       84              0       0       4     4                                       85              0       0       4     4                                       96              0       0       4     4                                       99              0       0       4     4                                       101             0       0       4     4                                       102             0       0       4     4                                       103             0       0       4     4                                       104             0       0       4     4                                       105             0       0       4     4                                       106             0       0       4     4                                       107             0       0       4     4                                       108             0       0       4     4                                       109             0       0       4     4                                       110             0       0       4     4                                       111             0       0       4     4                                       112             0       0       4     4                                       113             0       0       4     4                                       114             0       0       4     4                                       115             0       0       4     4                                       116             0       0       4     4                                       117             0       0       4     4                                       118             0       0       4     4                                       119             0       0       4     4                                       120             0       0       4     4                                       121             0       0       4     4                                       122             0       0       4     4                                       123             0       0       4     4                                       124             0       0       4     4                                       125             0       0       4     4                                       126             0       0       4     4                                       127             0       0       4     4                                       128             0       0       4     4                                       129             0       0       4     4                                       130             0       0       4     4                                       131             0       0       4     4                                       132             0       0       4     4                                       133             0       0       4     4                                       134             0       0       4     4                                       135             0       0       4     4                                       136             0       0       4     4                                       137             0       0       4     4                                       138             0       0       4     4                                       140             0       0       4     4                                       141             0       0       4     4                                       142             0       0       4     4                                       143             0       0       4     4                                       144             0       0       4     4                                       145             0       0       4     4                                       146             0       0       4     4                                       147             0       0       4     4                                       148             0       0       4     4                                       149             0       0       4     4                                       150             0       0       4     4                                       151             0       0       4     4                                       152             0       0       4     4                                       153             0       0       4     4                                       154             0       0       4     4                                       155             0       0       4     4                                       156             0       0       4     4                                       157             0       0       4     4                                       Comparison Compound                                                           N-ethyl-4-propyl-3-(propyl-                                                                   3       3       4     4                                       sulfonyl)-1H-1,2,4-triazole-                                                  1-carboxamide                                                                 No treatment    0       0       0     0                                       ______________________________________                                    

EXAMPLE 6

The plants indicated in the following Table II were treated in ahothouse prior to emergence with the compounds also listed in the tablein amounts of 3 kg of active agent per about 2.5 acres. Three weeksafter treatment the compounds of the invention exhibited a highselectivity together with an excellent action against the weed. Thecomparison compound did not have the selective properties.

    __________________________________________________________________________                                   Elope-                                                                        curus                                          Compound of the                                                                           po-    soy-                                                                             cot-                                                                             bush  myo-                                                                              Avena                                                                             Sen-                                                                             Se-   Echino-                                                                           Digit-                                                                            Cy-                                                                              Sor-               Invention No.                                                                             tatoe                                                                            maize                                                                             bean                                                                             ton                                                                              bean                                                                             pea                                                                              soides                                                                            fatua                                                                             ecio                                                                             taria                                                                            Poa                                                                              chloa                                                                             aria                                                                              perus                                                                            ghum               __________________________________________________________________________    1           10 10  10 10 10 10 0   0   0  0  0  0   0   0  0                  65          10 10  10 10 10 10 0   0   0  0  0  0   0   0  0                  67          10 10  10 10 10 10 0   0   0  0  0  0   0   0  0                  76          10 10  10 10 10 10 0   0   0  0  0  0   0   0  0                  Comparison Compound                                                           N-ethyl-4-propyl-                                                                          5  1   2  1  1  2  0   0   0  0  0  0   0   0  0                 3-(propylsulfonyl)-                                                           1H-1,2,4-triazole-1-                                                          carboxamide                                                                   Not treated 10 10  10 10 10 10 10  10  10 10 10 10  10  10 10                 __________________________________________________________________________

EXAMPLE 7

Young cotton plants in the stage where they have 5 to 7 leaves weretreated with the compounds indicated below in Table III. The compoundswere applied by spraying in an emulsion amount of 500 liters per about2.5 acres. After a few days the percentage of the dropped leaves wasdetermined. The results appear from the following table.

                  TABLE III                                                       ______________________________________                                                       Doses in g                                                     Compound of the                                                                              active agent/   defoliation                                    Invention No.  about 2.5 acres in %                                           ______________________________________                                        2              500             48.0                                           58             500             12.0                                                          2000            50.0                                           65             500             13.6                                           67             500             28.0                                           ______________________________________                                    

EXAMPLE 8

Young cotton plants in the stage where they have 5 to 7 leaves weretreated with the compound listed in the Table IV. For each treatmentfour plants were used which together had 24 to 25 leaves. The sprayamount was 500 liters per about 2.5 acres.

After a few days the percentage of the dropped leaves was determined.The results appear from the table.

                  TABLE IV                                                        ______________________________________                                                         Doses in g                                                   Compound of the  active agent/ defoliation                                    Invention No.    about 2.5 acres                                                                             in %                                           ______________________________________                                        2                 500          40.0                                           Comparison Compound                                                           Tri-n-butyl-trithio-                                                                            500          4.7                                            phosphate        2000          4.7                                            ______________________________________                                    

EXAMPLE 9

Willow implants in the stage of about 11 to 14 leaves and provided withtheir roots were treated with the compounds indicated below in Table Vin a manner as described in Example 8. For each treatment three plantswere used having altogether 24 to 25 leaves.

                  TABLE V                                                         ______________________________________                                                         Doses in g                                                   Compound of the  active agent/ defoliation                                    Invention No.    about 2.5 acres                                                                             in %                                           ______________________________________                                        2                 500          15.4                                           67               2000          61.5                                           68               2000          61.5                                           Comparison compound                                                           Tri-n-butyl-trithio-                                                          phosphate         500          7.7                                            ______________________________________                                    

EXAMPLE 10

Cotton plants in the stage of 6 to 8 developed leaves were treated withthe compounds indicated below in Table VI. The spray amount was 500liters per about 2.5 acres. For each treatment four plants were usedhaving together 28 leaves. After a few days the percentage of thedropped leaves was determined. The results appear from the followingtable.

                  TABLE VI                                                        ______________________________________                                                         Doses in g                                                   Compound of the  active agent/ defoliation                                    Invention No.    about 2.5 acres                                                                             in %                                           ______________________________________                                         2               2000          71.4                                           74               2000          59.3                                           80               2000          55.6                                           ______________________________________                                    

EXAMPLE 11

Cotton plants in the stage of 6 to 7 developed leaves were treated withthe compounds indicated in Table VII. For each treatment four plantswere used with a total of 25 to 26 meters. The spray amounts used were500 liters per about 2.5 acres. After a few days the percentage of thedropped leaves was determined.

The results appear from the following table.

                  TABLE VII                                                       ______________________________________                                                         Doses in g                                                   Compound of the  active agent/ defoliation                                    Invention No.    about 2.5 acres                                                                             in %                                           ______________________________________                                         2               2000          72                                             58               2000          76                                             73               2000          88                                             84               2000          72                                             88               2000          80                                             ______________________________________                                    

EXAMPLE 12

The compounds appearing from the following Table VIII were applied asaqueous emulsions or suspensions in a concentration of active agent of0.04%.

These compounds were sprayed in doses of 4 mg of sprayed amount per cm²into the tops of Petri dishes. To the thus formed spray deposits 25adult Mediterranean fruit flies (Ceratitis capitata) per dish wereexposed in the closed dishes under conditions of long-day duration.Criteria for the activity forms the mortality of the flies in percentageafter 24 hours. The following table shows a comparison of the thusdetermined mortality percentages.

                  TABLE VIII                                                      ______________________________________                                        Compound of the                                                                             Concentration of                                                                             Mortality in %                                   Invention No. active agent in %                                                                            after 24 hours                                   ______________________________________                                         2            0,04           100                                               3            0,04           100                                               4            0,04            68                                               5            0,04            95                                               20           0,04           100                                               21           0,04            90                                               22           0,04            52                                               23           0,04            90                                               24           0,04            45                                               25           0,04            80                                               26           0,04            75                                               27           0,04            95                                               28           0,04            75                                               29           0,04            60                                               30           0,04            56                                               31           0,04            52                                               32           0,04            20                                               52           0,04           100                                               57           0,04            79                                               73           0,04           100                                               74           0,04           100                                               86           0,04           100                                               87           0,04           100                                               89           0,04           100                                              144           0,04           100                                              147           0,04           100                                              158           0,04           100                                              159           0,04           100                                              160           0,04           100                                              Untreated                     0                                               ______________________________________                                    

EXAMPLE 13

The inventive compounds were applied as aqueous emulsions or suspensionswith an active agent concentration of 0.04%.

With these active agent preparations the tops and bottoms of Petridishes were sprayed with doses of 4 mg per cm². In the thus-formeddeposits juvenile specimens of the German cockroach (Blattellagermanica) were exposed in closed Petri dishes under conditions oflong-day duration. For each dish there were used ten of the cockroacheswhich were 12 to 17 days old and they were exposed for a time of 48hours.

The criterion for the activity was the mortality of the cockroaches inpercentages after 48 hours. The following table shows the mortalitypercentage rate.

                  TABLE IX                                                        ______________________________________                                        Compound of the                                                                             Concentration of                                                                             Mortality in %                                   Invention No. active agent in %                                                                            after 48 hours                                   ______________________________________                                         2            0,04           100                                               3            0,04           100                                               4            0,04           100                                               5            0,04           100                                              20            0,04           100                                              21            0,04           100                                              22            0,04           100                                              23            0,04           100                                              24            0,04            20                                              25            0,04           100                                              26            0,04           100                                              27            0,04            80                                              28            0,04           100                                              29            0,04           100                                              30            0,04           100                                              31            0,04           100                                              32            0,04           100                                              52            0,04           100                                              57            0,04           100                                              73            0,04           100                                              74            0,04           100                                              86            0,04           100                                              87            0,04           100                                              89            0,04           100                                              144           0,04           100                                              147           0,04           100                                              155           0,04           100                                              156           0,04           100                                              157           0,04           100                                              158           0,04           100                                              159           0,04           100                                              160           0,04           100                                              ______________________________________                                    

EXAMPLE 14

The compounds indicated below in Table X were used as aqueous emulsionsor suspensions in a concentration of active agent of 0.04%. Thesecompositions were then sprayed on potted broad beans (Vicia faba) sothat the plants were dripping wet. The plants had before been infestedheavily with the black bean louse (Aphis fabae).

The plants were then stored for 48 hours in the laboratory underconditions of long-day duration. The criterion for the activity was themortality of the lice in percentage after 48 hours. The following tableshows a comparison of the found mortality percentages.

                  TABLE X                                                         ______________________________________                                        Compound of the                                                                             Concentration of                                                                             Mortality in %                                   Invention No. active agent in %                                                                            after 48 hours                                   ______________________________________                                        2             0,04           100                                              3             0,04           100                                              4             0,04           100                                              5             0,04           100                                              20            0,04           100                                              21            0,04           100                                              22            0,04            60                                              23            0,04            90                                              24            0,04            90                                              25            0,04           100                                              26            0,04            90                                              27            0,04            95                                              28            0,04            90                                              29            0,04           100                                              30            0,04           100                                              31            0,04           100                                              32            0,04           100                                              52            0,04           100                                              57            0,04           100                                              73            0,04           100                                              74            0,04           100                                              86            0,04           100                                              87            0,04           100                                              89            0,04           100                                              144           0,04           100                                              147           0,04           100                                              155           0,04           100                                              156           0,04           100                                              157           0,04           100                                              158           0,04           100                                              159           0,04           100                                              160           0,04           100                                              ______________________________________                                    

EXAMPLE 15

The compound of the invention indicated in Table XI and two comparisoncompounds were applied as aqueous suspensions in an active agentconcentration of 0.0012%. These compositions were applied at a dose of 4mg of spray per cm² to the bottoms and tops of Petri dishes. In the thusformed deposits juvenile specimens of the German cochroach (Blattellagermanica) were exposed in closed Petri dishes under conditions oflong-day duration. For each dish there were used ten of the cockroacheswhich were 12 to 17 days old and they were exposed for a time of 48hours. The criterion for the activity was the mortality of thecochroaches in percentages after 48 hours. The following table shows themortality percentages obtained.

                  TABLE XI                                                        ______________________________________                                                      Concentration of                                                                            Mortality in %                                    Compound No.  active agent in %                                                                           after 48 hours                                    ______________________________________                                        2             0.0012        100                                               Comparison compound                                                           o-isopropoxyphenyl-                                                           methylcarbamate                                                                             0.0012        90                                                2,2-dimethyl-1,3-benzo-                                                       dioxol-4-yl-methylcarba-                                                      mate          0.0012        90                                                ______________________________________                                    

EXAMPLE 16

The compound of the invention indicated below in Table XII and thecomparison compound were applied as aqueous suspensions in an activeagent concentration of 0.00025%.

These compositions were sprayed in doses of 4 mg of spray amount per cm²into the tops and bottoms of Petri dishes. To the thus formed spraydeposits ten specimens per Petri dish were exposed of the Asiatic cottonleaf bug (Dysdercus cingulatus) in closed Petri dishes under conditionsof a long-day duration. The lice were exposed for 48 hours. They were inthe juvenile stage, that is in third skin-shedding stage.

The criterion for the activity was the mortality of the leaf bugs inpercentages after 48 hours. The following table shows a comparison ofthe mortality percentages found:

                  TABLE XII                                                       ______________________________________                                        Compound of the                                                                             Concentration of                                                                            Mortality in %                                    Invention No. active agent in %                                                                           after 48 hours                                    ______________________________________                                        2            0.00025        95                                                Comparison compound                                                           1-naphthyl-methyl-                                                            carbamate    0.00025        60                                                ______________________________________                                    

EXAMPLE 17

The compounds of the invention and the comparison compounds shown in thefollowing Table XIII were applied as aqueous emulsion at the indicatedconcentration. These compositions were sprayed at doses of 4 mg of sprayamount per cm² into the tops and bottoms of Petri dishes. To the formedspray deposit ten specimens per Petri dish of the Asiatic cotton leafbug (Dysdercus cingulatus) were exposed in the closed Petri dishes underconditions of a long-day duration. The exposure was for 42 hours and theinsects were used in a juvenile stage, that is, in the thirdskin-shedding stage.

The criterion for the activity was the knockdown effect in percentageafter 1, 30 and 60 minutes as well as the mortality of the leaf bugsafter 42 hours.

                                      TABLE XIII                                  __________________________________________________________________________                           Knock-Down-effect in %                                                                     Mortality                                 Compound of the                                                                             Concentration of                                                                       after        in %                                      Invention No. active agent in %                                                                      1 min.                                                                            30 min.                                                                            60 min.                                                                           after 42 hrs.                             __________________________________________________________________________    2             0,01     100 100  100 100                                                      0,009   100 100  100 100                                       52            0,01     --  100  100 100                                                      0,005   --  --   100 100                                       Comparison compound                                                           2-methoxycarbonyl-1-methyl-                                                                 0,01     100 100  100 100                                       nonyl-dimethylphosphate                                                                      0,005   --  100  100 100                                       5-benzyl-3-furylmethyl(±)-                                                               0,01     --   95   95  85                                       cis,trans-chrysanthemate                                                                     0,005   --  --   30   85                                       __________________________________________________________________________

EXAMPLE 18 Seed Treatment of Barley Against Helminthosporium Spec.

Barley seeds were seeded into plant pots filled with earth. The seedswere infested by the Helminthosporium gramineum. The seeded material waspartly untreated and partly treated as shown in Table I and was left forgermination at a temperature below +16° C. After emergence illuminationof the plants with light was effected for 12 hours daily. After about 5weeks the infested plants were counted and in the same manner the totalof the emerged plants. The fungicidal action was computed as follows:##EQU1##

                  TABLE XIV                                                       ______________________________________                                        Compound of the                                                                             g of active agent                                               Invention No. per 100 kg     % action                                         ______________________________________                                         2            20             --                                                             50             100                                               4            20             69                                                             50             94                                                7            20             54                                                             50             90                                               19            20             --                                                             50             90                                               20            20             97                                                             50             100                                              21            20             82                                                             50             93                                               25            20             67                                                             50             90                                               28            20             --                                                             50             70                                               29            20             --                                                             50             70                                               30            20             87                                                             50             98                                               31            20             56                                                             50             79                                               32            20             --                                                             50             58                                               33            20             --                                                             50             70                                               34            20             --                                                             50             87                                               35            20             --                                                             50             90                                               37            20             --                                                             50             94                                               38            20             --                                                             50             77                                               39            20             100                                                            50             100                                              52            20             --                                                             50             70                                               57            20             100                                                            50             --                                               58            20             95                                                             50             100                                              59            20             --                                                             50             70                                               60            20             --                                                             50             100                                              61            20             --                                                             50             100                                              64            20             --                                                             50             100                                              143           20             76                                                             50             87                                               ______________________________________                                    

EXAMPLE 19 Seed Treatment of Wheat Against Tilletia Caries

Oat seed material was contaminated with 3 g spores per kg of Tilletiacaries which is the agent causing a stinking smuts. Untreated grains andgrains treated as indicated in the following Table XV were pressed intoPetri dishes filled with moist loam with their hairy end and wereincubated at temperatures below +12° C. for a time of 3 days. The grainswere subsequently removed and the Petri dishes with the stinking smutsspores left behind were further incubated at about 12° C. After 10 daysthe spores were examined regarding germination. The fungicidal activitywas determined as follows: ##EQU2##

                  table XV                                                        ______________________________________                                        Compound of the                                                                             g of active agent                                               Invention No. per 100 kg     % action                                         ______________________________________                                        4             10             78                                                             20             93                                               19            10             --                                                             20             90                                               28            10             --                                                             20             90                                               29            10             --                                                             20             90                                               30            10             --                                                             20             90                                               31            10             68                                                             20             100                                              32            10             27                                                             20             100                                              33            10             --                                                             20             70                                               34            10             --                                                             20             72                                               35            10             --                                                             20             87                                               36            10             --                                                             20             87                                               37            10             --                                                             20             82                                               38            10             85                                                             20             94                                               40            10             --                                                             20             90                                               59            10             --                                                             20             90                                               61            10             --                                                             20             70                                               74            10             --                                                             20             90                                               82            10             --                                                             20             90                                               83            10             --                                                             20             90                                               88            10             --                                                             20             90                                               89            10             --                                                             20             90                                               90            10             --                                                             20             90                                               91            10             --                                                             20             90                                               92            10             --                                                             20             90                                               95            10             --                                                             20             90                                               96            10             --                                                             20             90                                               97            10             --                                                             20             90                                               127           10             --                                                             20             90                                               128           10             --                                                             20             90                                               129           10             --                                                             20             90                                               130           10             --                                                             20             90                                               133           10             --                                                             20             90                                               134           10             --                                                             20             90                                               135           10             --                                                             20             90                                               136           10             --                                                             20             90                                               137           10             --                                                             20             90                                               138           10             --                                                             20             90                                               144           10             50                                                             20             90                                               145           10             92                                                             20             90                                               146           10             12                                                             20             90                                               147           10             53                                                             20             90                                               149           10             --                                                             20             90                                               150           10             --                                                             20             90                                               ______________________________________                                    

EXAMPLE 20 Spray Treatment of Rice Seedlings Against Piricularia Oryzae

Young rice plants were tripped to be dripping wet with the compoundsgiven in the following Table XVI in the concentrations also indicated.After the spray deposits had been dried the treated plants and alsountreated plants were inoculated in a hothouse in a humid atmosphere at+25° to +27° C. The inoculation was effected by spraying with asuspension of spores in an amount of about 200,000/ml of the Piriculariaoryzae which is the agent causing the left spot disease. After 5 days itwas determined which percentage of the leaf surface had been infected.From these infection figures the fungicidal activity was determined asfollows: ##EQU3##

                  TABLE XVI                                                       ______________________________________                                        Compound of the                                                                            % of active agent                                                Invention No.                                                                              (sprayed dripping wet)                                                                         % action                                        ______________________________________                                        2            0,1              91                                                           0,02             65                                                           0,004            --                                              16           0,1              80                                                           0,02             --                                                           0,004            --                                              20           0,1              85                                                           0,02             --                                                           0,004            --                                              33           0,1              65                                                           0,02             --                                                           0,004            --                                              35           0,1              65                                                           0,02             --                                                           0,004            --                                              52           0,1              90                                                           0,02             --                                                           0,004            --                                              60           0,1              70                                                           0,02             --                                                           0,004            --                                              61           0,1              91                                                           0,02             58                                                           0,004            --                                              65           0,1              92                                                           0,02             57                                                           0,004            --                                              67           0,1              100                                                          0,02             60                                                           0,004            --                                              68           0,1              90                                                           0,02             --                                                           0,004            --                                              69           0,1              93                                                           0,02             45                                                           0,004            --                                              70           0,1              89                                                           0,02             --                                                           0,004            --                                              71           0,1              93                                                           0,02             55                                                           0,004            --                                              72           0,1              87                                                           0,02             --                                                           0,004            --                                              73           0,1              98                                                           0,02             80                                                           0,004            45                                              74           0,1              97                                                           0,02             75                                                           0,004            45                                              75           0,1              97                                                           0,02             87                                                           0,004            73                                              76           0,1              93                                                           0,02             80                                                           0,004            65                                              77           0,1              98                                                           0,02             87                                                           0,004            60                                              78           0,1              93                                                           0,02             75                                                           0,004            45                                              79           0,1              90                                                           0,02             --                                                           0,004            --                                              80           0,1              90                                                           0,02             --                                                           0,004            --                                              81           0,1              90                                                           0,02             --                                                           0,004            --                                              82           0,1              90                                                           0,02             --                                                           0,004            --                                              83           0,1              90                                                           0,02             --                                                           0,004            --                                              85           0,1              99                                                           0,02             87                                                           0,004            80                                              86           0,1              96                                                           0,02             20                                                           0,004            10                                              88           0,1              80                                                           0,02             35                                                           0,004            20                                              89           0,1              87                                                           0,02             --                                                           0,004            --                                              91           0,1              94                                                           0,02             87                                                           0,004            62                                              92           0,1              91                                                           0,02             73                                                           0,004            31                                              96           0,1              100                                                          0,02             89                                                           0,004            54                                              100          0,1              75                                                           0,02             69                                                           0,004            --                                              101          0,1              94                                                           0,02             62                                                           0,004            12                                              128          0,1              98                                                           0,02             65                                                           0,004            30                                              129          0,1              98                                                           0,02             50                                                           0,004            25                                              132          0,1              99                                                           0,02             50                                                           0,004            57                                              133          0,1              100                                                          0,02             89                                                           0,004            65                                              134          0,1              100                                                          0,02             85                                                           0,004            78                                              135          0,1              100                                                          0,02             100                                                          0,004            93                                              136          0,1              100                                                          0,02             80                                                           0,004            70                                              137          0,1              100                                                          0,02             80                                                           0,004            30                                              138          0,1              99                                                           0,02             86                                                           0,004            75                                              140          0,1              83                                                           0,02             --                                                           0,004            --                                              141          0,1              67                                                           0,02             --                                                           0,004            --                                              142          0,1              71                                                           0,02             17                                                           0,004            --                                              143          0,1              90                                                           0,02             --                                                           0,004            --                                              144          0,1              90                                                           0,02             --                                                           0,004            --                                              145          0,1              90                                                           0,02             --                                                           0,004            --                                              146          0,1              90                                                           0,02             --                                                           0,004            --                                              155          0,1              90                                                           0,02             --                                                           0,004            --                                              156          0,1              90                                                           0,02             --                                                           0,004            --                                              ______________________________________                                    

EXAMPLE 21 Spray Treatment of Tomato Seedlings Against Botrytis Cinerea

Young tomatoe plants were sprayed so as to be dripping wet with thecompounds indicated in the following Table XVII at the concentrationlikewise indicated. After drying of the spray deposit the treated plantsand also untreated plants were inoculated by spraying with a suspensionof spores (about 1 million spores per ml of a fruit juice solution) ofBotrytis cinera which is the agent causing the gray mold. Theinoculation was effected in a hot house in a wet atmosphere at about 20°C. After the collapse of the untreated plants (the infestation in theseplants was 100%) the degree of infestation of the treated plants wasdetermined and the fungicidal action was calculated as follows: ##EQU4##

                  TABLE XVII                                                      ______________________________________                                        Compound of the                                                                            % of active agent                                                Invention No.                                                                              (sprayed dripping wet)                                                                         % activity                                      ______________________________________                                        20           0.025            50                                              59           0.025            72                                              64           0.025            78                                              ______________________________________                                    

EXAMPLE 22 Threshold Concentration Test Regarding Root Gall Nematodes(Meloidogyne Sp.)

A 20% powder composition of active agents was distributed uniformly in asoil which had been heavily infested with root gall nematodes. After awaiting time of 3 days the treated soil was spread out in two ceramicvessels of a capacity of 0.5 liters and 10 grains of cucumber seeds ofthe type "Guntruud" were laid into each dish. There followed agermination time of 28 days in a hothouse at a temperature of 24° to 27°C. The cucumber roots were then washed out and were examined in a waterbath regarding nematode infestation. The reduction of infestation by thecompounds of the invention as compared with untreated controls wasdetermined in percentage as appears from Table XVIII. This table alsoshows the compounds of the invention, the amounts, and the reduction ininfestation.

Nematocidal activity was calculated as follows:

    A-B/A·100

wherein A is the infestation in the untreated control material and B isthe infestation after treatment.

    ______________________________________                                        Threshold concentration test                                                  Test namatode: Meloidogyne sp.                                                                Concentration of active agent                                                 in mg/liter of earth                                          Compound of the Invention No.                                                                   200 mg   100 mg   50 mg                                     ______________________________________                                         3                100      100      92                                         4                100      100      98                                        21                100      100      100                                       22                100      100      100                                       23                100      100      93                                        24                100      100      100                                       25                100      98       50                                        26                100      97       96                                        27                100      100      98                                        28                100      93       63                                        29                100      99       57                                        30                100      100      71                                        31                100      97       93                                        32                99       98       --                                        33                100      100      95                                        34                92       69       42                                        35                95       95       64                                        36                100      99       93                                        37                100      99       --                                        38                97       53       --                                        44                100      100      --                                        52                93       97       81                                        59                100      95       --                                        63                100      42       --                                        ______________________________________                                    

EXAMPLE 23 Leaf Treatment of Grapevines Against Plasmopara Viticola

Young grapevines having 5 to 8 leaves were treated so as to be drippingwet with the compounds listed in Table XIX at the concentration alsoindicated so as to be dripping wet. After drying of the spray depositsthe bottom side of the leaves was sprayed with an aqueous suspension ofsporangia of the fungus (about 20,000 per ml). The plants were thenimmediately subjected to incubation in a hothouse at a temperature of22° to 24° C. and in a maximum humidity atmosphere. Starting with thesecond day the air humidity was reduced for 3 to 4 days to a normallevel (30 to 70% saturation) and was then kept for 1 day on a watervapor saturation. Subsequently, the percentage portion of fungusinfected surface was determined for each leaf and the average wascalculated for each treatment to determine the fungicidal action on thebases of the following equation: ##EQU5##

                  TABLE XIX                                                       ______________________________________                                        Compound of the                                                               Invention No. % of active agent                                                                            % activity                                       ______________________________________                                         71           0.025          48                                               128           0.025          100                                              130           0.025          75                                               132           0.025          92                                               133           0.025          77                                               134           0.025          83                                               139           0.025          91                                               140           0.025          99                                               141           0.025          98                                               142           0.025          99                                               ______________________________________                                    

EXAMPLE 24 Leaf Treatment of Squash Plants Against ErysipheCichoracearum

Young squash plants were sprayed dripping wet with the compounds listedin Table XX below and at the concentration indicated. After drying ofthe spray deposit the plants were inoculated by dusting with dry mildewspores of Erysiphe cichoracearum. The incubation was carried out at 24°C. and after a week the surface infested with mildew was determined inpercentage relative to the total leaf surface.

The fungicidal activity was calculated as follows: ##EQU6##

                  TABLE XX                                                        ______________________________________                                        Compound of the                                                               Invention No.                                                                              % of active material                                                                          % activity                                       ______________________________________                                        67           0.025           97                                               68           0.025           85                                               72           0.025           90                                               74           0.025           100                                              78           0.025           90                                               103          0.025           70                                               146          0.025           92                                               147          0.025           94                                               154          0.025           90                                               ______________________________________                                    

TABLE 25 Seed Treatment of Oats on Acres in the Open Air AgainstUstilago Avenae

Oat seed material was dipped into a suspension of the spores of Ustilagoavenae which is the agent causing the oat smuts. The seed material wasthen exposed in a vacuum desiccator to a repeated change fromatmospheric to subatmospheric pressure. After drying of the seedmaterial the material was treated with the compounds stated in Table XXIbelow which were applied as a powdery composition. Ten weeks afterseeding the diseased panicles were counted and the activity wascalculated according to the formula ##EQU7##

                  TABLE XXI                                                       ______________________________________                                        Compound of the                                                                             g of active agent                                               Invention No. per 100 kg     % activity                                       ______________________________________                                        29            10             55                                                             20             --                                               59            10             82                                                             20             --                                               63            10             70                                                             20             --                                               ______________________________________                                    

Without further analysis, the foregoing will so fully reveal the gist ofthe present invention that others can, by applying current knowledge,readily adapt it for various applications without omitting featuresthat, from the standpoint of prior art, fairly constitute essentialcharacteristics of the generic or specific aspects of this invention.

What is claimed as new and desired to be protected by Letters Patent isset forth in the appended claims.
 1. 1,2,3-triazole carboxylic acidamides of the formula ##STR21## in which R₁ is C₁ -C₁₀ -alkyl, C₂ -C₈-alkenyl or alkinyl or is aryl-C₁ -C₃ -alkyl which may be substituted inone or several places by C₁ -C₆ -alkyl and/or halogen and/or C₁ -C₆-alkoxy and/or nitro and/or trifluoromethyl,R₂ is hydrogen or C₁ -C₁₀alkyl in which the chain may be interrupted in one or several places byoxygen- or sulfur atoms and which may be substituted by halogen, R₃ andR₄ are the same or different and are hydrogen, C₁ -C₁₀ alkyl, C₁ -C₁₀alkyl which is substituted by halogen or C₁ -C₃ -alkoxy, C₂ -C₈ -alkenylor alkinyl, aryl-C₁ -C₃ -alkyl which may be substituted in one orseveral places by C₁ -C₆ -alkyl and/or halogen and/or C₁ -C₆ -alkoxyand/or nitro and/or trifluoromethyl, a C₃ -C₈ cyclo aliphatichydrocarbon group which may also be substituted in one or several placesby C₁ -C₆ -alkyl, or an aromatic hydrocarbon group which may besubstituted in one or several places by C₁ -C₆ alkyl and/or halogenand/or C₁ -C₆ -alkoxy and/or nitro and/or trifluoromethyl, or wherein R₃and R₄ together with the adjoining nitrogen atom conconstitute a 3 to7-member ring which may include further oxygen, sulfur or nitrogen atomsand wherein n is 0, 1 or 2, or an isomeric mixture from any of thelisted compounds.
 2. The 1,2,3-triazole carboxylic acid amides of claim1 whereinR₁ is alkyl of 1 carbon atom or is aryl-C₁ -C₃ -alkyl which maybe substituted by chlorine, R₂ is hydrogen, methyl, ethyl, propyl,isopropyl, butyl or tert.-butyl, R₃ is alkyl, alkenyl or alkinyl of upto 6 carbon atoms or cyclo alkyl and which groups may be substituted bychlorine or methoxy, R₄ is alkyl, alkenyl or alkinyl with up to 6 carbonatoms or cyclo alkyl which may be substituted by chlorine or methoxy oris aryl-C₁ -C₃ -alkyl which may be substituted by chlorine or methyl, oris an aromatic hydrocarbon group which may be substituted by halogen ormethyl or wherein R₃ and R₄ together with the adjoining nitrogen atomform a morpholino-, piperidino-, pyrrolidino- or hexamethyleniminogroup, and wherein n is
 2. 3. The 1,2,3-triazole carboxylic acid amidesof claim 1 whereinR₁ is methyl, ethyl, propyl, allyl or propino-2-yl, R₂is hydrogen, methyl, ethyl, propyl, butyl or tert.-butyl, R₃ is hydrogenor methyl, R₄ is methyl and wherein n is
 0. 4. The 1,2,3-triazolecarboxylic acid amides of claim 1 whereinR₁ is alkyl of 1 to 10 carbonatoms, allyl, 2-methylallyl, propino-2-yl or aryl-C₁ -C₃ -alkyl, whichlatter may be substituted by chlorine, R₂ is hydrogen, methyl, ethyl,propyl, isopropyl, butyl, sec.-butyl, isobutyl, or tert.-butyl, R₃ ishydrogen, alkyl, alkenyl or alkinyl of up to 6 carbon atoms, R₄ isalkyl, alkenyl or alkinyl of up to 6 carbon atoms, and wherein n is 0.5. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dipropylamide. 6.The composition of claim 1 which is4-methyl-5-methylthio-1,2,3-triazole-1(2,3)-carboxylic aciddimethylamide.
 7. The composition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid methylamide.
 8. Thecomposition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid anilide.
 9. Thecomposition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid ethylamide.
 10. Thecomposition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid propylamide.
 11. Thecomposition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid butylamide.
 12. Thecomposition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid cyclohexylamide. 13.The composition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid (2-methylanilide).14. The composition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid-(2-chloroanilide).15. The composition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid (3-methylanilide).16. The composition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid (4-methylanilide).17. The composition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid-(3-chloroanilide).18. The composition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid-(4-chloroanilide).19. The composition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)carboxylic acid-allylamide.
 20. Thecomposition of claim 1 which is4-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide. 21.The composition of claim 1 which is4-ethylthio-1,2,3-triazole-1(2,3)-carboxylic acid methylamide.
 22. Thecomposition of claim 1 which is4-propylthio-1,2,3-triazole-1(2,3)-carboxylic acid methylamide.
 23. Thecomposition of claim 1 which is4-isopropylthio-1,2,3-triazole-1(2,3)-carboxylic acid methylamide. 24.The composition of claim 1 which is4-butylthio-1,2,3-triazole-1(2,3)-carboxylic acid methylamide.
 25. Thecomposition of claim 1 which is4-(1-methylpropylthio)-1,2,3-triazole-1(2,3)-carboxylic acidmethylamide.
 26. The composition of claim 1 which is4-allylthio-1,2,3-triazole-1(2,3)-carboxylic acid methylamide.
 27. Thecomposition of claim 1 which is4-isobutylthio-1,2,3-triazole-1(2,3)-carboxylic acid methylamide. 28.The composition of claim 1 which is4-(2-propinylthio)-1,2,3-triazole-1(2,3)-carboxylic acid methylamide.29. The composition of claim 1 which is4-benzylthio-1,2,3-triazole-1(2,3)-carboxylic acid methylamide.
 30. Thecomposition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide.31. The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid methylamide. 32.The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid ethylamide. 33.The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid propylamide. 34.The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid butylamide. 35.The composition of claim 1 which is4-methylsulfinyl-1,2,3-triazole-1(2,3)-carboxylic acid methylamide. 36.The composition of claim 1 which is4-methylsulfinyl-1,2,3-triazole-1(2,3)-carboxylic acid ethylamide. 37.The composition of claim 1 which is4-methylsulfinyl-1,2,3-triazole-1(2,3)-carboxylic acid propylamide. 38.The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid anilide.
 39. Thecomposition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid cyclohexlamide.40. The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(4-chloroanilide).
 41. The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(4-methylanilide).
 42. The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid-allylamide. 43.The composition of claim 1 which is4-methyl-5-methylthio-1,2,3-triazole-1(2,3)-carboxylic acid methylamide.44. The composition of claim 1 which is4-methylsulfinyl-1,2,3-triazole-1(2,3)-carboxylic acid butylamide. 45.The composition of claim 1 which is4-methylsulfinyl-1,2,3-triazole-1(2,3)-carboxylicacid-(4-methylanilide).
 46. The composition of claim 1 which is4-methylsulfinyl-1,2,3-triazole-1(2,3)-carboxylicacid-(4-chloroanilide).
 47. The composition of claim 1 which is4-methylsulfinyl-1,2,3-triazole-1(2,3)-carboxylic acid allylamide. 48.The composition of claim 1 which is4-methylsulfinyl-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide.49. The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide. 50.The composition of claim 1 which is4-isopropylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid methylamide.51. The composition of claim 1 which is4-isopropylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide.52. The composition of claim 1 which is4-isopropylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide.53. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid methylamide. 54.The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide.55. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide. 56.The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid ethylamide. 57.The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-propyl)-amide.
 58. The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-propyl)-amide.
 59. The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid-N-ethylanilide.60. The composition of claim 1 which is4-isopropylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-N-ethylanilide.
 61. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid-N-ethylanilide.62. The composition of claim 1 which is4-isopropylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-propyl)-amide.
 63. The composition of claim 1 which is4-butylthio-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide.
 64. Thecomposition of claim 1 which is4-isobutylthio-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide. 65.The composition of claim 1 which is4-butylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide. 66.The composition of claim 1 which is4-butylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide. 67.The composition of claim 1 which is4-isobutylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide.68. The composition of claim 1 which is4-isobutylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide.69. The composition of claim 1 which is4-ethylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide. 70.The composition of claim 1 which is4-ethylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide. 71.The composition of claim 1 which is4-(1-methylpropylsulfonyl)-1,2,3-triazole-1(2,3)carboxylic aciddimethylamide.
 72. The composition of claim 1 which is4-benzylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide. 73.The composition of claim 1 which is4-butylthio-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide.
 74. Thecomposition of claim 1 which is4-(1-methylpropylsulfonyl)-1,2,3-triazole-1(2,3)-carboxylic aciddiethylamide.
 75. The composition of claim 1 which is4-benzylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide.76. The composition of claim 1 which is4-ethylthio-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide.
 77. Thecomposition of claim 1 which is4-ethylthio-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide.
 78. Thecomposition of claim 1 which is4-isobutylthio-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide. 79.The composition of claim 1 which is4-(1-methylpropylthio)-1,2,3-triazole-1(2,3)-carboxylic aciddimethylamide.
 80. The composition of claim 1 which is4-(1-methylpropylthio)-1,2,3-triazole-1(2,3)-carboxylic aciddiethylamide.
 81. The composition of claim 1 which is4-benzylthio-1,2,3-triazole-1(2,3)-carboxylic acid dimethylamide. 82.The composition of claim 1 which is4-benzylthio-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide.
 83. Thecomposition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid propylamide. 84.The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid butylamide. 85.The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid isopropylamide.86. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dibutylamide. 87.The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid pyrrolidide. 88.The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid piperidide. 89.The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid diallylamide. 90.The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid morpholide. 91.The composition of claim 1 which is4-butylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-propyl)-amide.
 92. The composition of claim 1 which is4-isobutylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-propyl)-amide.
 93. The composition of claim 1 which is4-(1-methylpropylsulfonyl)-1,2,3-triazole-1-(2,3)-carboxylicacid-(N-ethyl-N-propyl)-amide.
 94. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-butyl)-amide.
 95. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dipentylamide.96. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-cyclohexyl)-amide.
 97. The composition of claim 1 whichis 4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic aciddiisopropylamide.
 98. The composition of claim 1 which is4-ethylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-propyl)-amide.
 99. The composition of claim 1 which is4-ethylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dipropylamide.100. The composition of claim 1 which is4-ethylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dibutylamide. 101.The composition of claim 1 which is4-butylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dipropylamide.102. The composition of claim 1 which is4-butylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dibutylamide. 103.The composition of claim 1 which is4-(1-methylpropylsulfonyl)-1,2,3-triazole-1(2,3)-carboxylic aciddibutylamide.
 104. The composition of claim 1 which is4-isobutylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dipropylamide.105. The composition of claim 1 which is4-isobutylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dibutylamide.106. The composition of claim 1 which is4-(1-methylpropyl)-sulfonyl-1,2,3-triazole-1(2,3)-carboxylic aciddipropylamide.
 107. The composition of claim 1 which is4-(1-methylpropyl)-sulfonyl-1,2,3-triazole-1(2,3)-carboxylic aciddiisopropylamide.
 108. The composition of claim 1 which is4-butylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-butyl)-amide.
 109. The composition of claim 1 which is4-isobutylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-butyl)-amide.
 110. The composition of claim 1 which is4-(1-methylpropyl)-sulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl)-N-butyl)-amide.
 111. The composition of claim 1 which is4-ethylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-cyclohexyl)-amide.
 112. The composition of claim 1 whichis 4-isopropylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid butylamide.113. The composition of claim 1 which is4-isopropylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dipropylamide.114. The composition of claim 1 which is4-butylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-cyclohexyl)-amide.
 115. The composition of claim 1 whichis 4-(1-methylpropyl)-sulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-cyclohexyl)-amide.
 116. The composition of claim 1 whichis 4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic aciddiisobutylamide.
 117. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid dihexylamide.118. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-benzyl)-amide.
 119. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-isopropyl)-amide.
 120. The composition of claim 1 whichis 4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-N,N-hexamethyleneamide.
 121. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-N-(2-cyanoethyl)-anilide.
 122. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid-N-methyl-anilide.123. The composition of claim 1 which is4-ethylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-butyl)-amide.
 124. The composition of claim 1 which is4-isopropylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-butyl)-amide.
 125. The composition of claim 1 which is4-isobutylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-cyclohexyl)-amide.
 126. The composition of claim 1 whichis 4-butylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-isopropyl)-amide.
 127. The composition of claim 1 whichis 4-isobutylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-isopropyl)-amide.
 128. The composition of claim 1 whichis 4-propylsulfinyl-1,2,3-triazole-1(2,3)-carboxylic acid diethylamide.129. The composition of claim 1 which is4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-bis(2-chloroethyl)-amide.
 130. The composition of claim 1 which is4-butylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-N-ethyl-N-benzyl-amide.
 131. The composition of claim 1 which is4-(1-methylpropyl)-sulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-benzyl)-amide.
 132. The composition of claim 1 which is4-isobutylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-benzyl)-amide.
 133. The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-butyl)-amide.
 134. The composition of claim 1 which is4-ethylthio-5-methyl-1,2,3-triazole-1(2,3)-carboxylic aciddimethylamide.
 135. The composition of claim 1 which is4-propylsulfonyl-5-methyl-1,2,3-triazole-1(2,3)-carboxylic aciddipropylamide.
 136. The composition of claim 1 which is4-propylsulfonyl-5-methyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-isopropyl)-amide.
 137. The composition of claim 1 whichis 4-(2-propinylthio)-5-methyo-1,2,3-triazole-1(2,3)-carboxylic aciddimethylamide.
 138. The composition of claim 1 which is4-methylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-isopropyl)-amide.
 139. The composition of claim 1 whichis 4-ethylsulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-isopropyl)-amide.
 140. The composition of claim 1 whichis 4-(1-methyl-propyl)-sulfonyl-1,2,3-triazole-1(2,3)-carboxylicacid-(N-ethyl-N-isopropyl)-amide.
 141. The composition of claim 1 whichis 4-ethylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic aciddiisopropylamide.
 142. The composition of claim 1 which is4-isobutylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic aciddiisopropylamide.
 143. The composition of claim 1 which is4-butylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic acid diisopropylamide.144. The composition of claim 1 which is5-methyl-4-propylsulfonyl-1,2,3-triazole-1(2,3)-carboxylic aciddiisopropylamide.
 145. The composition of claim 1 which is4-allylthio-5-methyl-1,2,3-carboxylic acid dimethylamide.
 146. Thecomposition of claim 1 which is4-(2-cyanoethylthio)-5-methyl-1,2,3-triazole-1(2,3)-carboxylic aciddimethylamide.
 147. The composition of claim 1 which is4-methylthio-5-propyl-1,2,3-triazole-1(2,3)-carboxylic aciddimethylamide.
 148. The composition of claim 1 which is5-ethyl-4-methylthio-1,2,3-triazole-1(2,3)-carboxylic aciddimethylamide.
 149. The composition of claim 1 which is5-isopropyl-4-methylthio-1,2,3-triazole-1(2,3)-carboxylic aciddimethylamide.
 150. The composition of claim 1 which is5-tert.-butyl-4-methylthio-1,2,3-triazole-1(2,3)-carboxylic aciddimethylamide.
 151. The composition of claim 1 which is4-isopropylthio-5-methyl-1,2,3-triazole-1(2,3)-carboxylic aciddimethylamide.
 152. A biocidal composition having herbicidal,insecticidal, acaricidal, fungicidal and/or nematocidal activitycomprising about 10 to 80% by weight of the active agents of claim 1 andabout 90 to 20% by weight of liquid or solid carrier materials which mayinclude up to about 20% by weight of surface active agents.